WO2005051670A1 - Matiere d'impression par jet d'encre - Google Patents

Matiere d'impression par jet d'encre Download PDF

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Publication number
WO2005051670A1
WO2005051670A1 PCT/JP2004/012112 JP2004012112W WO2005051670A1 WO 2005051670 A1 WO2005051670 A1 WO 2005051670A1 JP 2004012112 W JP2004012112 W JP 2004012112W WO 2005051670 A1 WO2005051670 A1 WO 2005051670A1
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WO
WIPO (PCT)
Prior art keywords
ink
pigment
receiving layer
ink receiving
recording material
Prior art date
Application number
PCT/JP2004/012112
Other languages
English (en)
Japanese (ja)
Inventor
Hiroaki Watanabe
Katsuaki Arai
Yasuro Yokota
Suguru Kashima
Original Assignee
Mitsubishi Paper Mills Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2003394439A external-priority patent/JP4559062B2/ja
Priority claimed from JP2004046107A external-priority patent/JP2005001373A/ja
Application filed by Mitsubishi Paper Mills Limited filed Critical Mitsubishi Paper Mills Limited
Priority to CN2004800212207A priority Critical patent/CN1826232B/zh
Priority to DE112004001339T priority patent/DE112004001339B4/de
Priority to US10/564,633 priority patent/US7713599B2/en
Publication of WO2005051670A1 publication Critical patent/WO2005051670A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/502—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording characterised by structural details, e.g. multilayer materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/502—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording characterised by structural details, e.g. multilayer materials
    • B41M5/506—Intermediate layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
    • B41M2205/12—Preparation of material for subsequent imaging, e.g. corona treatment, simultaneous coating, pre-treatments
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
    • B41M2205/38—Intermediate layers; Layers between substrate and imaging layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • B41M5/5218—Macromolecular coatings characterised by inorganic additives, e.g. pigments, clays

Definitions

  • the present invention relates to an ink jet recording material, and particularly to an ink jet recording material suitable for a pigment ink.
  • the ink jet recording method is a method of recording images, characters, and the like by flying fine droplets of ink by various operating principles and attaching the droplets to a recording material such as paper.
  • a recording material such as paper.
  • Ink jet printers and plotters have rapidly spread in recent years in various applications as hard copy creation devices for image information such as characters and various figures created by a computer.
  • color images formed by the multi-color ink jet method can achieve recording comparable to multi-color printing by the plate making method and printing by the color photographic method, and the number of copies can be reduced. In recent years, it has been widely used because it is cheaper than printing and photographic techniques.
  • pigment type inks have recently been used. It is known that pigment ink has little light deterioration and does not redissolve in water, so that it has better weather resistance and image storability than dye-type ink. However, since the colorant pigment in the ink is insoluble in the solvent unlike the dye, it is necessary to stably disperse the colorant pigment in the ink, and the ratio of the colorant pigment in the ink cannot be easily increased. Also, it is difficult to obtain a clear color development that has a high coloring efficiency like dye ink.
  • the demand for an ink jet recording material is inevitably increasing.
  • As a method of improving the absorbability of the pigment ink it is considered that the thickness of the ink receiving layer applied on the support is increased. In this method, the ink absorbency is improved, and the ink S penetrates deeply in the direction of the base paper, and the color developability decreases.
  • the pigment ink it is difficult to obtain a clear color compared to the dye ink, and therefore, when the ink penetrates deeply, the color forming property is significantly reduced. In the case of an ink jet recording material having no ink receiving layer, the decrease is further remarkable.
  • an ink jet recording material containing inorganic ultrafine particles which uses a synthetic silica mainly having a primary particle diameter of 3 nm to 30 nm mainly by a gas phase method.
  • An ink jet recording material is disclosed (for example, see Patent Documents 1 and 2).
  • a method has been proposed in which a coating layer containing inorganic ultrafine particles, polyvinyl alcohol and boric acid or a salt thereof is provided on an ink solvent non-absorbing support (for example, Patent Documents 3-5). reference). According to this method, when the dry coating amount of the coating layer is small, a force capable of obtaining the coating layer without causing cracks is low.
  • the coating solution is set on a support by heating the coating solution to room temperature or higher, or by cooling after coating, and setting the coating solution on a support. After forming a strong bond with the binder, drying must be performed, which lowers production efficiency and increases ink absorption even when the coating layer is thick. It may not be satisfactory.
  • a fumed silica, boric acid or borate, a polyether, or the like is provided on an ink solvent non-absorbing support. It has been proposed to sequentially stack a first ink receiving layer containing BURU alcohol, alumina or alumina hydrate, boric acid or borate, and a second ink receiving layer containing polyBULL alcohol (eg, And Patent Document 6). Although the ink absorption was improved by this method, it was still at an insufficient level.
  • a support having air permeability and ink solvent absorbability such as a paper support
  • an ink receiving layer having the above-described structure for example.
  • the binder component and the like in the coating layer do not fall into the support, cracking of the coating layer did not occur.
  • binder components and the like in the ink receiving layer fall into the paper support and cracks are easily generated on the surface of the ink receiving layer.
  • the pigment used in the ink receiving layer be an alumina hydrate (for example, see Patent Document 7).
  • Patent Document 7 alumina hydrate
  • a porous silica layer is provided as a lower layer, and an ink jet recording material having an anoremina or alumina hydrate-containing layer as an upper layer, an absorbent pigment-containing layer as a lower layer, and an upper layer as an upper layer. Recording materials provided with pseudo-boehmite have been proposed (for example, see Patent Documents 8 and 9).
  • an ink jet recording material has been proposed in which an undercoating layer containing a basic material is provided in order to improve the color developability of the ink, and a porous image-receiving layer made of fumed alumina is provided thereon (
  • the undercoat layer containing a basic material is composed only of a polymer component such as gelatin, the polymer component is coated by the water in the porous image receiving layer when the porous image receiving layer is coated. Since the porous image receiving layer swells and strains when the porous image receiving layer is dried, cracks may occur in the porous image receiving layer, resulting in a decrease in gloss and a decrease in pigment ink properties.
  • Patent Document 1 JP-A-10-203006 (pages 3-9)
  • Patent Document 2 JP-A-8-174992 (pages 3-6)
  • Patent Document 3 JP-A-7-76161 (page 2-3)
  • Patent Document 4 JP-A-10-193777 (pages 2-10)
  • Patent Document 5 Japanese Patent Application Laid-Open No. 2002-2094 (pages 2-10)
  • Patent Document 6 JP-A-2002-225423 (pages 2-7)
  • Patent Document 7 Japanese Patent Application Laid-Open No. 2002-79748 (pages 2-4)
  • Patent Document 8 JP-A-6-55829 (pages 2 to 3)
  • Patent Document 9 JP-A-7-89216 (pages 2-6)
  • Patent Document 10 JP-A-2002-331746 (pages 3-5)
  • An object of the present invention is to provide an ink jet recording material having both high absorption and coloring of a pigment ink without causing cracks on the surface of the ink receiving layer.
  • the coating liquid of the pigment layer and at least one or more ink receiving layers is sequentially applied and dried to obtain an ink jet recording material, and the average secondary particle diameter of the pigment contained in the pigment layer is obtained.
  • the force Sl m or more and 5 / im or less, and 50% by volume or more of the total volume of the pigment has a secondary particle diameter of 1.2 ⁇ m or more and 15 ⁇ m or less, and the first particle directly applied on the pigment layer.
  • the ink receiving layer contains at least inorganic ultrafine particles, a hydrophilic binder, and boric acid or borate, and the dry coating amount of the first ink receiving layer is 20% by mass of the dry coating amount of the pigment layer. % And not more than 120% by mass.
  • the pigment preferably has an oil absorption power Sl60mlZl00g or more and 320ml / lOOg or less represented by JIS K5101.
  • the pH of the coating liquid for the pigment layer is 8 or more and 11 or less, and the pH of the coating liquid for the first ink receiving layer is 3 or more and 5 or less.
  • the inorganic ultrafine particles contained in the first ink receiving layer are preferably alumina hydrate.
  • the second ink receiving layer applied on the first ink receiving layer is preferably made of an inorganic material. It is more preferable to contain alumina hydrate as ultrafine particles.
  • the inorganic ultrafine particles contained in the first ink receiving layer are preferably fumed silica and / or wet-process silica which has been pulverized until the average secondary particle diameter becomes 500 nm or less. It is more preferable that the second ink receiving layer applied on the first ink receiving layer contains alumina hydrate as inorganic ultrafine particles, which is contained in the first ink receiving layer. It is particularly preferable that the specific surface area force S of the fumed silica or the wet method silica by the BET method is smaller than the specific surface area of the alumina hydrate contained in the second ink receiving layer by the BET method.
  • At least one of the ink receiving layers contains basic polyaluminum hydroxide.
  • At least one ink receiving layer except the first ink receiving layer contains boric acid or borate.
  • the 75-degree specular glossiness defined by JIS P8142 of the inkjet recording material is 55% or more.
  • the ink jet recording material of the present invention has no cracks on the surface of the ink receiving layer, it is possible to have both high absorbency and color developability without dropping the pigment ink into cracks. It becomes.
  • the present inventors separate the solvent and the coloring material pigment in the pigment ink, distribute the coloring material pigment in the pigment ink near the surface of the ink receiving layer, It is thought that high absorption and improvement in color development can be achieved by penetrating the ink into the ink receiving layer.
  • the ink jet recording material of the present invention is characterized in that, when providing each ink receiving layer for improving the color developability of the pigment ink by distributing the coloring material pigment in the pigment ink near the surface of the ink receiving layer, the coating layer It is important to minimize the generation of cracks.
  • the inventors of the present invention have conducted intensive studies on a technique for eliminating the cracks on the surface of the ink receiving layer and separating the colorant pigment component and the solvent component in the pigment ink. As a result, a paper support having air permeability and ink solvent absorbency as a support was used.
  • the pigment has an average secondary particle diameter of 1 ⁇ m or more and 5 ⁇ or less, and 50% by volume or more of the total volume of the pigment has a secondary particle diameter of 1.2 ⁇ or more. / m or less, and the first ink receiving layer directly applied on the pigment layer contains at least inorganic ultrafine particles, a hydrophilic binder, and boric acid or borate, By making the dry coating amount of one ink receiving layer 20% by mass or more and 120% by mass or less of the dry coating amount of the pigment layer, it becomes possible to form the ink receiving layer without cracking on the pigment layer.
  • the pigment ink is a recording liquid comprising a colorant pigment, a dispersion solvent, other additives, and the like, and is not particularly limited.
  • the dispersion solvent may be any of water and various organic solvents.
  • the ink jet recording material according to the present invention uses a paper support having air permeability and ink solvent absorption as the support.
  • the paper support in the present invention include chemical pulp such as LBKP and NBK P, and mechanical pulp such as GP, PGW, RMP, TMP, CTMP, CMP and CGP.
  • Wood and pulp such as waste paper pulp such as pulp and DIP and conventionally known pigments as main components, and various additives such as knuckle and sizing agents, fixing agents, retention agents, cationizing agents, paper strength agents, etc.
  • base papers manufactured by various devices such as fourdrinier paper machines, round paper machine machines, twin wire paper machine machines, etc., and the base paper is further subjected to size pressing with starch, polybutyl alcohol, etc. You can give it.
  • the ink jet recording material of the present invention has an average secondary particle diameter of 1 ⁇ m or more and 5 ⁇ m or less and 50% by volume or more of the total volume of the pigment particles on the paper support.
  • a pigment layer containing a pigment having a size of not less than ⁇ m and not more than 15 ⁇ m is provided.
  • the secondary particles are particles formed by agglomeration of fine primary particles and existing in a dispersed state, and in the case of monodisperse particles, refer to the dispersed particle diameter.
  • the term "% by volume” refers to the ratio of the total volume of pigment particles having a particle diameter within a specified range to the total volume of pigment particles contained in the pigment layer.
  • the average secondary particle diameter and the volume% in the present invention are obtained from particle size distribution data measured by a particle size distribution meter using a laser diffraction 'scattering method.
  • the average secondary particle diameter of the pigment used in the pigment layer of the present invention is 1 ⁇ m or more and 5 ⁇ m or less. It is preferably from 1 ⁇ to 4 / im, particularly preferably from 1.2 ⁇ m to 3 ⁇ m.
  • the average secondary particle size of the pigment is smaller than 1 ⁇ m, the pigment layer is coated with the first ink receiving layer coating liquid in which the pigment and the like in the pigment layer are largely dropped onto the paper support. It is not possible to sufficiently suppress the drop of the indder component and the like in the ink receiving layer, and as a result, the coating layer of the ink receiving layer tends to crack.
  • the average secondary particle size of the pigment is larger than 5 ⁇ , the smoothness of the pigment layer is reduced, so that even when the ink receiving layer according to the present invention is provided on the pigment layer, a satisfactory surface gloss is obtained. I can't get it. Further, the gap between the pigment particles becomes too large, and the pigment layer cannot sufficiently suppress the drop of the binder component and the like in the ink receiving layer. As a result, the coating layer of the ink receiving layer easily cracks.
  • the pigment particles contained in the pigment layer have a secondary particle diameter of not less than 50% by volume of the total volume of the pigment particles and not less than 1.2 111 and not more than 15 111.
  • the pigment layer is included in the pigment layer. It is more preferable that 50% by volume or more of the total volume of the pigment particles have a secondary particle size of 1.5 ⁇ m or more and 10 ⁇ m or less. More preferably, the pigment particles having a secondary particle size of not less than 1.5 / im and not more than 10 / im are 65% by volume or more of the total volume of the pigment particles contained in the pigment layer.
  • oil absorption capacity measured by Pio IS K5101 is preferably 60 ml / 100 g or more and 320 ml / 100 g or less, more preferably 170 ml / 100 g or more and 300 ml / 100 g or less, and even more preferably 190 ml / 100 g or less. More than 280mlZl00g or less.
  • the water in the ink receiving layer coating solution is appropriately absorbed, so that the viscosity of the ink receiving layer coating solution is increased by increasing the concentration of the ink receiving layer coating solution.
  • Prevention of the inorganic ultrafine particles or the like from falling into the lower layer is preferable because cracks can be suppressed on the surface of the ink receiving layer and the ink absorbency can be improved.
  • a pigment layer is formed on a paper support.
  • the air permeability defined by JIS P8117 in the installed state is preferably 30 seconds or more and 1000 seconds or less. Preferably it is 50 seconds or more and 300 seconds or less.
  • one or more known white pigments can be used.
  • porous synthetic amorphous silica porous calcium carbonate, porous magnesium carbonate, porous alumina, and the like, which are preferred by porous inorganic pigments, due to cracks in the coating layer and balance of ink absorption.
  • porous synthetic amorphous silica is preferable.
  • the pigment layer contains, in addition to the pigment particles, an adhesive or the like, and further includes a cationic compound in addition to the above when applied to an ink jet recording system using both a pigment ink and a dye ink.
  • Additives include dye fixing agents, pigment dispersants, thickeners, flow improvers, surfactants, defoamers, foam inhibitors, release agents, foaming agents, penetrants, coloring dyes.
  • a coloring pigment, a fluorescent whitening agent, an ultraviolet absorber, an antioxidant, an antiseptic, an antibacterial agent, a waterproofing agent, a wetting force enhancer, a dry paper strength enhancer, and the like can be appropriately compounded.
  • the pigment layer of the present invention preferably further contains a binder.
  • the binder include starch derivatives such as oxidized starch, etherified starch, and phosphate ester starch; cellulose derivatives such as methinoresenorelose, canoleboxymethinoresenorelose, and hydroxyethenoresenorelose; polyvinyl alcohol Or polyvinyl alcohol derivatives such as silanol-modified polyvinyl alcohol; casein, gelatin and denatured products thereof, natural polymer resins such as soybean protein, pullulan, gum arabic, gum karaya, albumin or derivatives thereof, polyacrylamide, polyvinyl A vinyl polymer such as pyrrolidone, a hydrophilic binder such as alginic acid, polyethyleneimine, polypropylene glycol, polyethylene glycol, maleic anhydride or a copolymer thereof, a styrene-butadiene copolymer, Conjugated gen-
  • the compounding amount of the binder used in the pigment layer of the present invention is 570 parts by mass, and preferably 1050 parts by mass, based on 100 parts by mass of the total pigment particles.
  • the range of the dry coating amount of the pigment layer is 3 to 30 g / m 2 , more preferably 5 to 20 g / m 2 , and the dry coating amount of the pigment layer is within this range. This is preferable because ink absorption can be obtained more efficiently without reducing glossiness.
  • the ink jet recording material of the present invention is a layer directly applied on the pigment layer, contains inorganic ultrafine particles, a hydrophilic binder and boric acid or borate, and has a dry coating amount of the pigment layer.
  • the first ink-receiving layer which accounts for 20% by mass or more and 120% by mass or less of the dry coating amount, and one or more ink-receiving layers, if necessary, are sequentially laminated. With this configuration, it is possible to have both the high color developability and the ink absorbency of the pigment ink in which the cracks on the surface of the coating layer are eliminated.
  • the inorganic ultrafine particles in the ink jet recording material of the present invention refer to inorganic fine particles having an average secondary particle diameter of 500 nm or less when primary particles are aggregated to form secondary particles. In the case of monodispersed particles, it refers to inorganic fine particles having an average primary particle diameter of 500 nm or less.
  • JP-A-1-97678, JP-A-2-275510, JP-A-3-281383, JP-A-3-285814, JP-A-285815, JP-A-92183, JP-A-4-267180 Alumina hydrates such as pseudo-boehmite sol disclosed in Japanese Unexamined Patent Publications Nos.
  • Silica sol as if dispersed with a high-speed homogenizer, wet-milled to an average secondary particle diameter of less than 500 nm Rica, Kuti bets to Besides, smectite clay (JP-A 7 81210 JP) such as montmorillonite, Jirukoniazo Typical examples thereof include nore, chromia sol, yttria sol, ceria sol, iron oxide sol, zircon sol, aluminum oxide sol, and antimony oxide sol.
  • JP-A 7 81210 JP smectite clay
  • Jirukoniazo Typical examples thereof include nore, chromia sol, yttria sol, ceria sol, iron oxide sol, zircon sol, aluminum oxide sol, and antimony oxide sol.
  • the average primary particle diameter of the inorganic ultrafine particles in the present invention is defined as the diameter of a circle equal to the projected area of each of 100 primary particles present in a certain area by observing the fine particles with an electron microscope.
  • the average secondary particle diameter of the inorganic ultrafine particles is obtained by measuring the diluted dispersion with a particle size distribution analyzer using a laser diffraction 'scattering method.
  • alumina hydrate is preferable among the above inorganic ultrafine particles.
  • cracks are less likely to occur on the surface of the ink receiving layer, and the performance of separating the colorant pigment and the solvent of the pigment ink can be improved.
  • the alumina hydrate used in the present invention can be represented by the general formula Al 2 O ⁇ ⁇ .
  • the Alumina hydrates are classified into gibbsite, bayerite, calestlandite, boehmite, boehmite gel (pseudo-boehmite), diaspore, amorphous amorphous, etc. according to the difference in composition and crystal form.
  • ⁇ when the value of ⁇ is 1, it represents an alumina hydrate having a boehmite structure, and when ⁇ is more than 1 and less than 3, it represents an alumina hydrate having a pseudo-boehmite structure.
  • ⁇ is 3 or more, it represents an alumina hydrate having an amorphous structure.
  • alumina hydrates preferred in the present invention are those having a pseudo-boehmite structure in which at least ⁇ is more than 1 and less than 3.
  • acids are usually added to the dispersion.
  • acids include nitric acid, hydrochloric acid, hydrobromic acid, acetic acid, formic acid, ferric chloride, and aluminum chloride, but the present invention is not limited thereto.
  • the shape of the alumina hydrate used in the present invention may be any of a flat plate, a fibrous shape, a needle shape, a spherical shape, a rod shape, and the like.
  • the plate-like alumina hydrate has an average aspect ratio of 38, and preferably has an average aspect ratio of 316.
  • the aspect ratio is expressed as the ratio of “diameter” to “thickness” of a particle.
  • the diameter of a particle is equal to the projected area of the particle when the alumina hydrate is observed with an electron microscope. Represents the diameter of a new circle.
  • the alumina hydrate used in the present invention is produced by a known method such as hydrolysis of aluminum alkoxides such as aluminum isopropoxide, humidification of aluminum salt with alkali, hydrolysis of aluminate. can do.
  • the physical properties of alumina hydrate, such as particle diameter, pore diameter, pore volume, and specific surface area, should be controlled by conditions such as precipitation temperature, aging temperature, aging time, liquid pH, liquid concentration, and coexisting compounds. Can be.
  • JP-A-57-88074, JP-A-62-56321, JP-A-4-275917, JP-A-6-64918, and JP-A-7-105 Nos. 35, 7-267633, and U.S. Pat. No. 2,656,321 disclose a method for decomposing aluminum alkoxide in water. These aluminum alkoxides include isopropoxide, 2-butoxide and the like.
  • an alumina hydrate having an average primary particle diameter of 3 nm and 25 nm is preferable.
  • Particularly preferred average primary particle diameter is 5 nm to 20 nm.
  • the average secondary particle diameter in which these are connected is 50 nm to 200 nm.
  • the inorganic ultrafine particles contained in the first ink receiving layer of the present invention include a vapor-phase method and / or a wet method that is pulverized until the average secondary particle diameter becomes 500 nm or less.
  • fumed silica can be preferably used.
  • the fumed silica is also called dry silica, and is generally produced by a flame hydrolysis method.
  • a method is generally known in which tetrachlorosilane is produced by burning silicon and hydrogen together with oxygen.
  • silanes such as methyltrichlorosilane and trichlorosilane are also used alone.
  • the fumed silica is commercially available as QS type from Nippon Aerosil Co., Ltd., Arasil, and Tokuyama Co., Ltd.
  • the average primary particle diameter of the fumed silica used in the present invention is preferably 5 nm or more and 50 nm or less from the viewpoints of cracking of the coating layer of the first ink receiving layer, surface gloss, and coloring of the pigment ink. More preferably, it is 10 nm or more and 40 nm or less, particularly preferably 15 nm or more and 30 nm or less. Further, the BET specific surface area, coating layer cracking of the first ink-receiving layer, particularly preferably preferably from the viewpoint of in-click absorbent 30 m 2 / g or more 300 meters 2 / g or less device 40 m 2 / g or more and 150 m 2 / g or less is preferable.
  • the BET method referred to in the present invention is one of the methods for measuring the surface area of a powder by a gas-phase adsorption method, and is a method for determining the total surface area, that is, the specific surface area of an lg sample from an adsorption isotherm.
  • nitrogen gas is often used as the adsorbed gas, and a method of measuring the amount of adsorption from the pressure or volume change of the gas to be adsorbed is most often used.
  • the most prominent one for expressing the isotherm of multimolecular adsorption is the Brunauer, Emmett and Teller equation, which is called the BET equation and is widely used for determining the surface area.
  • the surface area can be obtained by calculating the amount of adsorption based on the BET equation and multiplying the area occupied by one adsorbed molecule on the surface.
  • fumed silica is used in the presence of a cationic compound so that the fumed silica has an average secondary particle diameter of 500 nm or less, preferably 50 to 400 nm, more preferably 50 to 400 nm.
  • those dispersed at 100 to 300 nm can be used.
  • a dispersion method a gas-phase method silica, a cationic compound and a dispersion medium are premixed by a conventional propeller stirring, a turbine type stirring, a homomixer type stirring or the like, and then a ball mill, a bead mill, a sand grinder or the like is used.
  • a pressure type disperser such as a media mill, a high-pressure homogenizer, an ultra-high-pressure homogenizer, an ultrasonic disperser, a thin-film rotating type disperser, or the like.
  • the wet method silica used in the first ink receiving layer is classified into a precipitation method silica and a gel method silica according to the production method.
  • Precipitated silica is produced by reacting sodium silicate and sulfuric acid under alkaline conditions, and the silica particles that have grown are agglomerated and settled, followed by filtration, washing with water, drying and pulverization.
  • Precipitated silica is commercially available, for example, as Epseal from Tosoh's Silica Co., Ltd. and as Toksir from Tokuyama Corporation.
  • Gel silica is produced by reacting sodium silicate and sulfuric acid under acidic conditions.
  • the fine particles dissolve and re-precipitate so as to combine the other primary particles, so that the clear primary particles disappear and form relatively hard and agglomerated particles having an internal void structure.
  • Tosoh Silica Co., Ltd. sells it as Nip Jiel, and Grace Japan Co., Ltd. sells it as siloids and silo jets.
  • wet-process silica pulverized to an average secondary particle diameter of 500 nm or less is used.
  • wet-process silica particles used in the present invention wet-process silica particles having an average primary particle size of 50 nm or less, preferably 340 nm, and an average aggregated particle size of 5 to 50 ⁇ m are used.
  • wet-process silica fine particles obtained by finely pulverizing the fine particles to an average secondary particle diameter of 500 nm or less, preferably about 50 to 400 nm in the presence of a cationic compound are used.
  • wet-process silica produced by a usual method has an average agglomerated particle diameter of 1 Pm or more, it is used after pulverized.
  • a pulverization method a wet dispersion method of mechanically pulverizing silica dispersed in an aqueous medium can be preferably used. At this time, the increase in the initial viscosity of the dispersion is suppressed, high-concentration dispersion becomes possible, and the pulverization 'dispersion efficiency is increased, so that the fine particles can be pulverized. It is preferred to use precipitated silica of m or more. By using a high-concentration dispersion, the productivity of recording paper is also improved. Oil absorption is measured based on the description in JIS K5101.
  • silica particles and a cationic compound are mixed in water (which is the first one of Dispersing device such as a sawtooth blade type disperser, a propeller blade type disperser, or a rotor-stator type disperser.
  • a predispersion is obtained using at least one of If necessary, an appropriate low boiling point solvent or the like may be added.
  • the solid concentration of the silica pre-dispersion is preferably as high as possible, but if the concentration is too high, it is impossible to disperse.
  • the preferable range is 15 to 40% by mass, more preferably 20 to 35% by mass. Then, by giving stronger mechanical means, a wet-process silica fine particle dispersion having an average secondary particle diameter of 500 nm or less can be obtained.
  • the mechanical means known methods can be employed, for example, a media mill such as a ball mill, a bead mill, and a sand grinder; a pressure disperser such as a high-pressure homogenizer and an ultra-high pressure homogenizer; an ultrasonic disperser; You can use force S etc.
  • a cationic polymer or a water-soluble metal compound can be used as the cationic compound used for dispersing the fumed silica and the wet silica.
  • the cationic polymer include polyethyleneimine, polydiallylamine, polyallylamine, alkylamine polymer, JP-A-59-20696, JP-A-59-33176, JP-A-59-33177, and JP-A-59-33177. No. 15508 8, No. 60-11389, No. 60-49990, No. 60-83882, No. 60-1098 No. 94, No. 62-198493, No. 63-49478, No. 63-115780, No. 63-2 80681, No.
  • cationic polymers having a tertiary amino group and a quaternary ammonium base described in No. 125411 and No. 10-193776 are preferably used.
  • a diarylamine derivative is preferably used as the cationic polymer.
  • the molecular weight of these cationic polymers is preferably about 2,000 to 100,000, and more preferably about 2,000,000.
  • water-soluble metal compound examples include a water-soluble polyvalent metal salt.
  • a compound composed of aluminum or a Group 4 metal of the periodic table eg, zirconium, titanium
  • Particularly preferred are water-soluble aluminum compounds.
  • water-soluble aluminum compounds for example, as inorganic salts, aluminum chloride or hydrate thereof, aluminum sulfate or hydrate thereof, ammonium alum and the like are known.
  • a basic polyaluminum hydroxide compound which is an inorganic aluminum-containing cationic polymer is known and is preferably used.
  • alumina hydrate is contained as the contained inorganic ultrafine particles.
  • alumina hydrate is used, higher surface gloss and higher gloss of a printed portion can be obtained, and coloring of the pigment ink can be improved.
  • the same alumina hydrate as that used for the first ink receiving layer can be used.
  • a gas phase method or wet method silica is used for the first ink receiving layer
  • alumina hydrate is used for the second ink receiving layer
  • the specific surface area of the fumed silica or wet silica used in the first ink receiving layer by the BET method is calculated from the specific surface area of the alumina hydrate used in the second ink receiving layer by the BET method. Is also preferably small.
  • BET specific surface area force of fumed silica or wet silica used in the first ink receiving layer is lower than BET specific surface area of alumina hydrate used in the second ink receiving layer. Due to the small size, the amount of binder components and the like in the second ink receiving layer falling into the first ink receiving layer is reduced, and the coating layer of the ink receiving layer has almost no adverse effect on ink absorbency. Is presumed to occur.
  • the first ink receiving layer may be made of a fumed silica or a wet-process silica ground to an average secondary particle diameter of 500 nm or less, respectively.
  • the content ratio of the fumed silica or the pulverized wet process silica in the first ink receiving layer (the total content ratio when used in combination) may be the same as that of the first ink receiving layer. 50% by mass or more based on the solid content is preferable, 70% by mass or more is more preferable, and especially 80% by mass or more is preferable.
  • the content ratio of alumina hydrate in the first or second ink receiving layer is preferably 50% by mass or more with respect to the total solid content in the first or second ink receiving layer. The above is more preferred, especially 80% by mass or more.
  • a hydrophilic binder that maintains the properties as a film, has high transparency, has high ink permeability, and is used.
  • the hydrophilic binder include starch derivatives such as oxidized starch, etherified starch, and phosphated starch; senorelose derivatives such as methylcellulose, canoleboxymethinoresenorelose, and hydroxyethinoresenorelose; Polyvinyl alcohol or polyvinyl alcohol derivatives such as silanol-modified polyvinyl alcohol; casein, gelatin and modified products thereof, natural polymer resins such as soybean protein, phenolol, gum arabic, gum karaya, albumin or derivatives of these, polyacrylic acid
  • vinyl polymers such as noreamide and polyvinylpyrrolidone, alginic acid, polyethyleneimine, polypropylene glycol, polyethylene glycol, maleic anhydride and copolymers thereof, and can
  • Cutting power S is not limited to these.
  • a polybutyl alcohol or a polybutyl alcohol derivative such as silanol-modified polybutyl alcohol is preferred.
  • particularly preferred among the polybutyl alcohols are those having a saponification degree of 80% or more, and more preferably a saponification degree of 88. / 0 or more 96. / 0 less than polybutyl alcohol.
  • the average weight is particularly preferably 2000 or more, more preferably 3000 or more.
  • the content of these hydrophilic binders is preferably 3 to 25% by mass in terms of the total dry solid content in terms of cracking of the coating layer and ink absorbability. There is Particularly preferred.
  • the content of the first ink receiving layer is preferably 8 to 25% by mass, more preferably 10 to 20% by mass.
  • the content is preferably 3 to 15% by mass, particularly preferably 4 to 10% by mass.
  • boric acid used in the first ink receiving layer in the present invention not only orthoboric acid but also metaboric acid, hypoboric acid and the like can be used.
  • the borate is preferably one of these soluble salts, specifically, Na B ⁇ -10H ⁇ , NaBOBO4 ⁇ 0 ⁇ ⁇ ⁇ ⁇ 5 ⁇ , ⁇ ⁇ ⁇
  • the ink receiving layer has two or more layers, it is preferable that at least one ink receiving layer excluding the first ink receiving layer contains boric acid or borate.
  • hydrophilic binder contained in the ink receiving layer is preferably 11 to 15% by mass, and more preferably 310 to 10% by mass.
  • the dry coating amount of the first ink receiving layer is determined by the dry coating amount of the pigment layer. 20% by mass or more and 120% by mass or less of the amount. More preferably, the content is 40% by mass or more and 100% by mass or less.
  • the ink receiving layer in the present invention may further contain a cationic compound for the purpose of improving fixability and water resistance of the pigment ink and the dye ink.
  • a cationic compound the compounds exemplified as the cationic compound used for dispersion of the above-mentioned fumed silica and wet silica can be used.
  • the use of basic polyaluminum hydroxide improves the separation performance of the colorant pigment and the solvent in the pigment ink, which is less likely to cause cracks in the coating layer, and improves the color development of the pigment ink.
  • the basic poly (aluminum hydroxide) is preferably contained in at least one of the ink receiving layers. However, in order to fix the pigment ink or the dye ink on the surface of the ink receiving layer, the ink which is the outermost surface is used. It is particularly preferable to include it in the receiving layer.
  • the basic polyaluminum hydroxide compound has a main component represented by the following general formula (1), (2) or (
  • n is an integer satisfying the relationship 0 ⁇ m ⁇ 3n.
  • the content of the basic polyaluminum hydroxide in the ink receiving layer is 0.1%.
  • cationic dye fixing agents cationic dye fixing agents, pigment dispersants, thickeners, flow improvers, viscosity stabilizers, pH adjusters, surfactants , Defoamers, foam inhibitors, mold release agents, foaming agents, penetrants, coloring dyes, coloring pigments, optical brighteners, ultraviolet ray absorbents, antioxidants, leveling agents, preservatives, anti-foaming agents
  • a water-proofing agent, a wet paper strength enhancer, a dry paper strength enhancer, and the like can be appropriately added as long as the object of the present invention is not impaired.
  • the dry coating amount of each ink receiving layer is not particularly limited, but the range of the dry coating amount of each ink receiving layer is in terms of ink absorbency and cracks of the coating layer.
  • the amount is 3 to 16 g / m 2 , more preferably 5 to 12 g / m 2 .
  • the pH of the pigment layer coating liquid is preferably 8 or more and 11 or less, and the pH of the first ink receiving layer coating liquid is preferably 3 or more and 5 or less. More preferably not P H of the pigment layer coating solution 8.5 to 11, P H of the first ink receiving layer coating solution is 3 or more 4.5 or less. This range is preferable because the amount of the binder and the inorganic ultrafine particles in the ink receiving layer falling into the pigment layer is reduced and the surface gloss is improved.
  • any basic material can be used for the pigment layer coating liquid used in the present invention, as long as it is compatible with the pigment layer coating liquid, and is added to the pigment layer coating liquid.
  • the pH of the coating solution of the pigment layer is appropriately adjusted.
  • water examples include hydroxides such as aluminum oxide and sodium hydroxide, carbonates such as sodium carbonate, amine compounds, and ammonia.
  • any acidic material can be used as long as it is compatible with the coating liquid for the ink receiving layer. By doing so, the pH of the coating liquid of the ink receiving layer is appropriately adjusted.
  • the basic material used include, for example, inorganic acids such as nitric acid, hydrochloric acid, hydrobromic acid, acetic acid, formic acid, lactic acid, citric acid, ferric chloride, and aluminum chloride, and organic acids.
  • the pigment layer and the ink receiving layer are formed by sequentially applying and drying each coating liquid on a support.
  • the method of coating when each layer is provided is not particularly limited, and a known coating method can be used.
  • the method of drying after coating the coating liquid is not particularly limited, and a known drying method can be used.
  • a method of blowing hot air, a method of irradiating infrared rays, or the like, may be used.
  • the drying method is preferably used because of good productivity.
  • the present invention after coating and drying the pigment layer or the ink receiving layer, it may be smoothed by calendering for the purpose of controlling flatness and further increasing the surface gloss.
  • the calendar processing device at that time include a Darros calendar, a super calendar, and a soft calendar.
  • the 75-degree specular glossiness of the inkjet recording material of the present invention measured by JIS-P8142 is 55. It is preferably at least / 0 and at most 80 ° / ⁇ . It is more preferably at least 60 ° / ⁇ and at most 80 ° / ⁇ , particularly preferably at least 65% and at most 80%.
  • the average secondary particle diameter and the secondary particle diameter of the pigment contained in the pigment layer are 1.2 to 15 / im.
  • the ratio to the total volume of the particles was measured by a laser light diffraction 'scattering method (Microtrac 9320HRA, manufactured by Leeds & Northrup).
  • Synthetic amorphous silica (average secondary particle diameter: 1.2 / m, oil absorption: 180 ml / 100g, secondary particle diameter: 1.2 to 15 ⁇ m, ratio of inorganic particles: 50% by volume) 100 parts using a homogenizer And dispersed in 400 parts of water, and mixed with 250 parts of a 10% aqueous solution of polyvinyl alcohol (completely cured, polymerization degree 1700) to prepare a pigment layer coating liquid 1 having a solid content of 16.7% and a pH of 6.4. did.
  • Synthetic amorphous silica (average secondary particle diameter 1.5 / m, oil absorption 130ml / 100g, ratio of inorganic particles with a secondary particle diameter of 1.2-15 ⁇ m: 80% by volume) 100 parts using a homogenizer Te is dispersed in 400 parts of water, to which 10% of polyvinyl alcohol (fully ⁇ , polymerization degree: 1700) was mixed with water solution 250 parts of a solid concentration of 16.7%, a P H6. 1 of the pigment layer coating solution 2 Prepared.
  • Synthetic amorphous silica (average secondary particle diameter: 4 xm, oil absorption: 250 ml / 100 g, ratio of inorganic particles having a secondary particle diameter of 1.215 zm: 100% by volume) 100 parts of water was mixed with 400 parts of water using a homogenizer. Disperse in this to 10. / 0 Polyvinyl alcohol (completely cured, polymerization degree 1700) aqueous solution 250 parts were mixed to prepare a pigment layer coating liquid 3 having a solid content concentration of 16.7% and a pH of 6.2.
  • Synthetic amorphous silica (average secondary particle diameter: 4 xm, oil absorption: 160 ml / 100 g, ratio of inorganic particles having a secondary particle diameter of 1.215 zm: 100% by volume) 100 parts of water was mixed with 400 parts of water using a homogenizer. The mixture was mixed with 250 parts of a 10% aqueous solution of polyvinyl alcohol (completely cured, polymerization degree: 1700) to prepare a pigment layer coating liquid 5 having a solid content of 16.7% and a pH of 5.8.
  • Synthetic amorphous silica (average secondary particle diameter: 4 ⁇ , oil absorption: 340 ml / 100 g, ratio of inorganic particles having a secondary particle diameter of 1.2-15 / im: 100% by volume) 100 parts of water was mixed using a homogenizer. The mixture was dispersed in 400 parts, and 250 parts of a 10% aqueous solution of polyvinyl alcohol (completely cured, polymerization degree: 1700) was mixed with the mixture to prepare a pigment layer coating liquid 6 having a solid content of 16.7% and a pH of 6.1.
  • Synthetic amorphous silica (average secondary particle diameter 4 beta m, oil absorption 160 ml / 100 g) 50 parts of synthetic amorphous silica (average secondary particle diameter 4 mu m, an oil absorption of 340ml / l00g) 50 parts were mixed
  • the average secondary particle diameter of the pigment contained in the pigment layer was 4 ⁇ m, and the proportion of inorganic particles with a secondary particle diameter of 1.215 ⁇ m was adjusted to 100% by volume of the total volume of the inorganic particles using a homogenizer. using dispersed in 400 parts of water, to which 10% of polyvinyl alcohol (fully ⁇ , polymerization degree 1700) water solution 250 parts of a mixture of a solid concentration 16. 7%, P H6. 1 of the pigment layer coating liquid 7 was prepared.
  • the oil absorption of the synthetic amorphous silica mixture used was 250 ml / 100 g.
  • ⁇ Pigment layer coating liquid 8 > 100 parts of sodium hydroxide 2 parts, synthetic amorphous silica (average secondary particle size 4 ⁇ , oil absorption 250 ml / 100 g, inorganic particles with secondary particle size 1.2-15 ⁇ : 100% by volume) the using Homoji Naiza dispersed in 400 parts of water, to which 10% of polyvinyl alcohol (fully ⁇ , polymerization degree: 1700) solution 250 parts of a mixture of a solid concentration 16. 9%, P H10. 5 pigment layer Coating solution 8 was prepared.
  • High white primary kaolin (average secondary particle diameter 1. 6 zm, oil absorption 40MlZl00g, the ratio of secondary particle diameter 1 2-15 zm of the inorganic particles:. 80 vol 0/0) 100 parts of sodium polyacrylate 0 1 part was dispersed in 150 parts of water using a homogenizer, and 250 parts of an 8% oxidized starch aqueous solution was mixed with the mixture to prepare a pigment layer coating liquid 9 having a solid content of 24% and a pH of 9.5.
  • Light calcium carbonate (average secondary particle size: 2.0 xm, oil absorption: 85 ml / l00g, secondary particle size: 1.2-15 ⁇ ⁇ , ratio of inorganic particles: 65% by volume) 100 parts, sodium polyacrylate 0. 2 parts were dispersed in 100 parts of water using a homogenizer, and 42 parts of 48% styrene-butadiene copolymer latex solids were mixed to prepare a pigment layer coating liquid 10 having a solids concentration of 49.7% and a pH of 9.8. did.
  • Synthetic amorphous silica (average secondary particle diameter 0.8 / m, oil absorption 110ml / 100g, ratio of inorganic particles with a secondary particle diameter of 1.2 to 15 ⁇ m: 20% by volume) 100 parts using a homogenizer And dispersed in 400 parts of water, and mixed with 250 parts of a 10% aqueous solution of polyvinyl alcohol (completely cured, polymerization degree 1700) to prepare a pigment layer coating liquid 11 having a solid content of 16.7% and a pH of 5.9. did.
  • Synthetic amorphous silica (average secondary particle diameter: 20 xm, oil absorption: 230 ml / 100 g, ratio of inorganic particles having a secondary particle diameter of 1.2 to 15 ⁇ m: 30% by volume) Divided into 00 parts and added to 10. / o polyvinyl alcohol (fully ⁇ , polymerization degree: 1700) solution 250 parts of a mixture of a solid concentration 16.7%, to prepare a pigment layer coating solution 12 of P H5. 8.
  • the following shows a synthesis example of alumina hydrate used for the ink receiving layer.
  • Raw materials used All products were commercial products and were used without purification.
  • a 3 L reactor was charged with 1200 g of ion-exchanged water and 900 g of isopropyl alcohol, and heated to 75 ° C. 408 g of aluminum isopropoxide was added, and the mixture was hydrolyzed at 75 ° C for 24 hours and at 95 ° C for 4 hours. Then, add 24 g of acetic acid, stir at 95 ° C for 40 hours, disperse using a saw-tooth blade type disperser, concentrate to a solid content of 16%, A dispersion of particulate alumina hydrate was obtained. The average secondary particle size of the alumina hydrate fine particles measured by a laser light diffraction-scattering method was 180 nm.
  • the sol was dried at room temperature and measured for X-ray diffraction, which showed a pseudo-boehmite structure. Further, the average primary particle diameter was measured by a transmission electron microscope, and it was about 20 nm, and it was an alumina hydrate having a plate-like pseudo-boehmite structure with an acetate ratio of 6.
  • the BET specific surface area, average pore radius, pore volume at a pore radius of lnm 30 nm, and pore volume at a pore radius of 2 nm 10 nm were measured by the nitrogen adsorption / desorption method, and found to be 136 m 2 / g 5.8, respectively. It was 0.54 ml / g and 0.50 ml / g.
  • Porous silica (average primary particle diameter 12 nm, average secondary particle diameter 120 nm, specific surface area by BET method 300 m 2 / g, dispersity 0.3) 100 parts are dispersed in 480 parts of water using a homogenizer, and 10 parts of % poly Bulle alcohol ( ⁇ degree 88./., polymerization degree 2400) 200 parts of an aqueous solution, a mixture of 20 parts of an aqueous solution of 4% boric acid, a solid concentration of 15. 1% P H4. 7 ink-receiving layer coating solution 2 was prepared.
  • Vapor-phase method silica (average primary particle diameter: 12 nm, average secondary particle diameter: 120 nm, specific surface area by BET method: 300 m 2 / g, dispersity: 0.3) 100 parts are dispersed in 500 parts of water using a homogenizer. A 200% aqueous solution of 10% polybutyl alcohol (degree of polymerization: 88./., The polymerization degree: 2400), 20 parts of 4Q / o boric acid aqueous solution, and 20 parts of 25% basic polyaluminum hydroxide aqueous solution are mixed, and the solid fraction is mixed. An ink receiving layer coating solution 5 having a concentration of 15.0% and a pH of 4.2 was prepared.
  • Example 1 40% colloidal silica (monodispersed particles, average primary particle diameter 80 nm) is mixed with 200 parts of 10% polyvinyl alcohol aqueous solution (88% of degree of polymerization, 2400 degree of polymerization) aqueous solution and 10 parts of 2% aqueous sodium borate solution, An ink receiving layer coating solution 7 having a concentration of 34.7% and a pH of 9.2 was prepared.
  • Example 1 40% colloidal silica (monodispersed particles, average primary particle diameter 80 nm) is mixed with 200 parts of 10% polyvinyl alcohol aqueous solution (88% of degree of polymerization, 2400 degree of polymerization) aqueous solution and 10 parts of 2% aqueous sodium borate solution.
  • An ink receiving layer coating solution 7 having a concentration of 34.7% and a pH of 9.2 was prepared.
  • Example 1 so that the pigment layer coating solution 1 in the dry solids 12 g / m 2 on the support 1 prepared above, coating with an air knife coater, and dried with hot air. Then applied to made in-click-receiving layer coating solution 1 in the dry solids 9GZm 2 by an air knife coater on top of the pigment layer was formed by drying with hot air, row-,, implement a soft calender treatment The ink jet recording material of Example 1 was produced.
  • Example 2 The ink jet recording material of Example 2 was produced under the same conditions as in Example 1 except that the pigment layer coating liquid 2 was used instead of using the pigment coating liquid 1.
  • Example 3
  • Example 3 The ink jet recording material of Example 3 was produced under the same conditions as in Example 1 except that the pigment layer coating liquid 3 was used instead of the pigment layer coating liquid 1.
  • Example 4 The ink jet recording material of Example 4 was produced under the same conditions as Example 1 except that the pigment layer coating liquid 4 was used instead of using the pigment layer coating liquid 1.
  • Example 5 The ink jet recording material of Example 5 was produced under the same conditions as Example 1 except that the pigment layer coating liquid 5 was used instead of using the pigment layer coating liquid 1.
  • Example 6 The ink jet recording material of Example 6 was produced under the same conditions as Example 1 except that the pigment layer coating liquid 6 was used instead of using the pigment layer coating liquid 1.
  • Example 7 The ink jet recording material of Example 7 was produced under the same conditions as Example 1 except that the pigment layer coating liquid 7 was used instead of the pigment layer coating liquid 1 in Example 1.
  • Example 8 The ink jet recording material of Example 8 was produced under the same conditions as Example 1 except that the pigment layer coating liquid 8 was used instead of using the pigment layer coating liquid 1.
  • Example 9 The ink jet recording material of Example 9 was produced under the same conditions as in Example 1 except that the pigment layer coating liquid 9 was used instead of the pigment layer coating liquid 1.
  • Example 10 The ink jet recording material of Example 10 was produced under the same conditions as in Example 1 except that the pigment layer coating liquid 10 was used instead of the pigment layer coating liquid 1.
  • Example 1 was the same as Example 1 except that the pigment layer coating liquid 3 was used instead of the pigment layer coating liquid 1, and the ink receiving layer coating liquid 3 was used instead of the ink receiving layer coating liquid 1.
  • Example under the same conditions as Eleven ink jet recording materials were produced.
  • Example 1 was repeated except that the pigment layer coating liquid 7 was used instead of the pigment layer coating liquid 1 and the ink receiving layer coating liquid 3 was used instead of the ink receiving layer coating liquid 1.
  • the inkjet recording material of Example 12 was produced under the same conditions as described above.
  • Example 1 was the same as Example 1 except that the pigment layer coating liquid 8 was used instead of the pigment layer coating liquid 1, and the ink receiving layer coating liquid 2 was used instead of the ink receiving layer coating liquid 1. Under the same conditions as above, an ink jet recording material of Example 13 was produced.
  • Example 1 was the same as Example 1 except that the pigment layer coating liquid 8 was used instead of using the pigment layer coating liquid 1, and the ink receiving layer coating liquid 3 was used instead of using the ink receiving layer coating liquid 1. Under the same conditions as above, an ink jet recording material of Example 13 was produced.
  • Example 1 was the same as Example 1 except that the pigment layer coating liquid 10 was used instead of the pigment layer coating liquid 1, and the ink receiving layer coating liquid 3 was used instead of the ink receiving layer coating liquid 1.
  • the ink-jet recording material of Example 15 was produced under the same conditions as described above.
  • Example 1 was the same as Example 1 except that the pigment layer coating liquid 8 was used instead of the pigment layer coating liquid 1, and the ink receiving layer coating liquid 5 was used instead of using the ink receiving layer coating liquid 1.
  • the ink-jet recording material of Example 16 was produced under the same conditions as described above.
  • Example 17 The dry solids 12 g / m 2 of the pigment layer coating solution 8 of Example 14 to 17. 5g / m 2, the dry solids 9GZm 2 of the ink-receiving Sonurieki 3 dry solids 3. 5 g / m An inkjet recording material of Example 17 was produced under the same conditions as in Example 14 except that the composition was changed to 2 .
  • Example 1 was the same as Example 1 except that the pigment layer coating liquid 8 was used instead of using the pigment layer coating liquid 1, and the ink receiving layer coating liquid 7 was used instead of using the ink receiving layer coating liquid 1. Under the same conditions as above, an ink jet recording material of Example 19 was produced.
  • An ink jet recording material of Comparative Example 3 was produced under the same conditions as in Example 1 except that the pigment layer coating liquid 11 was used in Example 1 instead of using the pigment layer coating liquid 1.
  • An ink jet recording material of Comparative Example 4 was produced under the same conditions as in Example 1 except that the pigment layer coating liquid 12 was used instead of the pigment layer coating liquid 1 in Example 1.
  • Example 5 The same conditions as in Example 1 except that the pigment layer coating liquid 8 was used instead of using the pigment layer coating liquid 1 in Example 1, and the ink receiving layer coating liquid 4 was used instead of using the ink receiving layer coating liquid 1. Thus, an inkjet recording material of Comparative Example 5 was produced.
  • Example 1 The same conditions as in Example 1 except that the pigment layer coating liquid 11 was used instead of the pigment layer coating liquid 1 in Example 1, and the ink receiving layer coating liquid 4 was used instead of using the ink receiving layer coating liquid 1. Compare with The ink jet recording material of Example 6 was produced.
  • Example 7 A comparison was made under the same conditions as in Example 1 except that the pigment layer coating liquid 3 was used instead of the pigment layer coating liquid 1 in Example 1, and the ink receiving layer coating liquid 6 was used instead of using the ink receiving layer coating liquid 1.
  • the ink jet recording material of Example 7 was produced.
  • the dry solid content of the pigment layer coating liquid 3 of Example 3 was adjusted to 12 g / m 2 as the dry solid content of 18.5 g / m 2 , and the ink receiving layer coating liquid 1 of 9 g / m 2 was dried solid content.
  • An inkjet recording material of Comparative Example 8 was produced under the same conditions as in Example 3 except that the material was changed to 2.5 g / m 2 .
  • the dry solid content of the pigment layer coating liquid 3 of Example 3 was adjusted to 12 g / m 2 to a dry solid content of 8.4 g / m 2 , and the ink receiving layer coating liquid 1 of 9 g / m 2 was dried solid.
  • An inkjet recording material of Comparative Example 9 was produced under the same conditions as in Example 3 except that the amount was changed to 12.6 g / m 2 .
  • Example 1-119 Comparative Example 1-1-9 MC-10000 manufactured by Seiko Epson Co., Ltd., a printer using pigment ink (using pigment ink, printer setting: MC glossy paper, neat) An image was printed using the above method, and the presence or absence of cracks on the surface of the ink receiving layer and the ink absorbency were evaluated.
  • the images used for evaluation consisted of solid printing of each color of black, cyan, magenta, yellow, blue, red, and green, and patterns in which white characters were provided.
  • the ink absorptivity was evaluated by visually observing the uniformity of the solid printing portion, the boundary between adjacent solid printing portions and the sharpness of outline characters, and was expressed by a numerical value of 1 to 10. . 1 is the most in The higher the value, the better the ink absorbency. A value of 10 indicates the best ink absorbency. The results are shown in "Ink Absorption" in Table 1.
  • the average secondary particle diameter of the pigment contained in the pigment layer is 1 ⁇ m or more and 5 am or less, and 50% by volume or more of the total 2 ⁇ m or more and 15 zm or less and the ink receiving layer is made of at least inorganic ultrafine particles and hydrophilic binder.
  • a coating liquid containing boric acid and boric acid are sequentially applied to a paper support such that the dry coating amount of the ink receiving layer is 20% by mass or more and 120% by mass or less of the dry coating amount of the pigment layer.
  • the dried ink jet recording material By using the dried ink jet recording material, it was possible to obtain an ink jet recording material having both absorptivity and coloring property of the pigment ink without causing cracks on the surface of the ink receiving layer even when drying by heat.
  • the oil absorption of the pigment particles is 160 ml / 100 g and 320 ml / 100 g
  • the absorbency is improved
  • the surface gloss is improved by using a pigment layer of pH 811 and an ink receiving layer of pH 3-5.
  • the separation properties of the colorant pigment and the solvent in the pigment ink are further improved, and the ink jet ink has better surface gloss, ink absorption and color development.
  • the recording material was obtained.
  • Comparative Example 1 since only the pigment layer was used, sufficient color developability was not obtained.
  • Comparative Example 2 when only the ink receiving layer was used, the absorption of the pigment ink was insufficient. Cracking of the coating layer occurred.
  • Comparative Example 3 the secondary particles of the pigment particles contained in the pigment layer had a small secondary particle size, so the ink absorption was not sufficient, but the secondary particles of the pigment particles contained in the pigment layer were too large.
  • Example 4 cracks occurred on the surface of the ink receiving layer, and the surface gloss and the color development were reduced. Further, in Comparative Examples 5, 6, and 7, since the ink receiving layer did not contain boric acid, cracks could not be prevented.
  • the pigment receiving layer has both the absorbability and the coloring property of the pigment ink without causing cracks on the surface of the ink receiving layer.
  • the pigment receiving layer has both the absorbability and the coloring property of the pigment ink without causing cracks on the surface of the ink receiving layer.
  • a mixture of 50 parts of LBKP and 50 parts of NBSP was beaten to a freeness of 300 ml to prepare a pulp slurry.
  • 0.5% by weight of alkyl ketene dimer to pulp as a sizing agent 1.0% by mass of pulp to polyacrylamide as a paper strength enhancer, 2.0% of pulp to cationized starch, 2.0% of polyamide epichlorohydrin
  • the resin was added 0.5% to pulp and diluted with water to a 1% slurry.
  • the slurry was paper-machined to a basis weight of 170 g / m 2 using a fourdrinier paper machine to prepare a paper substrate.
  • the surface of the paper substrate (the side on which the pigment layer and the ink receiving layer were provided) had a density of 0.918 gZcm.
  • 3 low-density polyethylene 100% resin, 5% A polyethylene resin composition in which natase-type titanium is uniformly dispersed is melted at 320 ° C , extruded and coated at a rate of 200 m / min to a thickness of 20 ⁇ m, and then using a fine-roughened cooling roll.
  • a support 2 having a surface glossiness of 60% and having air permeability and ink solvent absorbability was prepared.
  • the pigment was converted to synthetic amorphous silica (average secondary particle diameter: 1.2 zm, oil absorption: 180 ml / 100 g, ratio of inorganic particles having a secondary particle diameter of 1.2—15 / im: 50 (% By volume), except that the coating liquid was prepared in the same manner as the pigment layer coating liquid 13.
  • the pH of the coating solution was 6.6.
  • the pigment was converted to a synthetic amorphous silica (average secondary particle diameter 4.3 / m, oil absorption 260ml / 100g, secondary particle diameter 1.2-15 / im). 100% by volume), and prepared in the same manner as for the pigment layer coating liquid 13.
  • the pH of the coating solution was 6.5.
  • Light calcium carbonate (average secondary particle size: 2.5 ⁇ , oil absorption: 90 ml / 100 g, ratio of inorganic particles with a secondary particle size of 1.2 to 15 ⁇ m: 70% by volume) 100 parts of water using a homogenizer Dispersed in 100 parts, 42 parts of 48% styrene-butadiene copolymer latex, 50 parts of 8% starch oxide aqueous solution and 0.3 part of surfactant were mixed to obtain a solid content of 42.5% and pH 9.6.
  • a pigment layer coating liquid 16 was prepared.
  • the pigment is made of synthetic amorphous silica (average secondary particle diameter 0.8 zm, P and oil amount 110 ml Z100 g, ratio of inorganic particles with a secondary particle diameter 1.2-15 zm: 20% by volume) ) was prepared in the same manner as for the pigment layer coating liquid 13.
  • the pH of the coating solution was 6.5.
  • the pigment was converted to a synthetic amorphous silica (average secondary particle diameter 6.0 / im, oil absorption 220ml / 100g, secondary particle diameter 1.2-15 / im of inorganic particles: 100% by volume), and prepared in the same manner as for the pigment layer coating liquid 13.
  • the pH of the coating solution was 6.7.
  • an ink receiving layer coating liquid 8 having a solid content of 15.0% and a pH of 4.1 was prepared.
  • the average secondary particle diameter of the fumed silica fine particles measured by laser single light diffraction / scattering method was 500 nm.
  • the fumed silica of the ink receiving layer coating liquid 8 was changed to the fumed silica having an average primary particle diameter of 16 nm and a specific surface area of 130 m 2 / g by the BET method, the same as the ink receiving layer coating liquid 8 was used.
  • the pH of the coating solution was 4.2.
  • the average secondary particle diameter of the fumed silica fine particles measured by the laser light diffraction 'scattering method was 40 Onm.
  • the fumed silica of the ink receiving layer coating liquid 8 was changed to the fumed silica having an average primary particle diameter of 30 nm and a specific surface area of 50 m 2 / g by the BET method, the same as the ink receiving layer coating liquid 8 was used.
  • the average secondary particle diameter of the fumed silica fine particles measured by the laser light diffraction 'scattering method was 500 nm.
  • the fumed silica of the ink receiving layer coating liquid 8 was changed to the fumed silica having an average primary particle diameter of 12 nm and a specific surface area of 200 m 2 / g by the BET method, the same as the ink receiving layer coating liquid 8 was used.
  • P H of the coating liquid 4. was 3.
  • the average secondary particle diameter of the fumed silica fine particles was 35 Onm.
  • alumina hydrate having a pseudo-boehmite structure (average primary particle diameter 15 nm, specific surface area 160 m 2 / g by BET method) are added, and sawtooth blade type dispersion is added. Using a machine, a 20.2% alumina hydrate dispersion was prepared.
  • alumina hydrate dispersion 500 parts of the alumina hydrate dispersion thus obtained, 10 parts of a 4% boric acid aqueous solution, 100 parts of 8% polybutyl alcohol (degree of saponification 88%, average polymerization degree 3500), 25% aqueous solution of basic polyaluminum hydroxide Forty parts, 0.3 part of a surfactant and 54 parts of water were mixed to prepare a coating liquid 13 for an ink receiving layer having a solid content concentration of 17.0% and a pH of 3.1.
  • the average secondary particle diameter of the alumina hydrate fine particles measured by the laser light diffraction / scattering method was 150 nm.
  • the ink receiving layer coating liquid 13 was prepared in the same manner as the ink receiving layer coating liquid 13 except that boric acid was not used.
  • the pH of the coating solution was 3.1.
  • Example 13 was coated with an air knife coater so that the dry coating amount was 8 g / m 2 , and dried to produce an ink jet recording material of Example 20.
  • Example 21 The ink jet recording material of Example 21 was produced under the same conditions as in Example 20, except that the pigment layer coating liquid 14 was used instead of the pigment layer coating liquid 13.
  • the air permeability defined by JIS P8117 of the sheet after coating with the pigment layer was 150 seconds.
  • Example 22 The inkjet recording material of Example 22 was produced under the same conditions as in Example 20, except that the pigment layer coating liquid 15 was used instead of the pigment layer coating liquid 13.
  • the air permeability of the sheet after coating with the pigment layer was 80 seconds as defined by JIS P8117.
  • Example 23 The inkjet recording material of Example 23 was produced under the same conditions as in Example 20, except that the pigment layer coating liquid 16 was used instead of the pigment layer coating liquid 13.
  • the air permeability defined by JIS P8117 of the sheet after coating with the pigment layer was 270 seconds.
  • Example 24 was carried out under the same conditions as in Example 20 except that the ink receiving layer coating liquid 9 was used instead of using the ink receiving layer coating liquid 8 to apply the first ink receiving layer. Ink jet recording material was prepared.
  • Example 25 was carried out under the same conditions as in Example 20 except that the ink receiving layer coating liquid 10 was used instead of using the ink receiving layer coating liquid 8 to apply the first ink receiving layer in Example 20. Ink jet recording material was prepared.
  • Example 26 was carried out under the same conditions as in Example 20 except that the ink receiving layer coating liquid 11 was used instead of the ink receiving layer coating liquid 8 to apply the first ink receiving layer in Example 20. Ink jet recording material was prepared.
  • Example 27
  • Example 27 was carried out under the same conditions as Example 20 except that the ink receiving layer coating liquid 12 was used instead of using the ink receiving layer coating liquid 8 to apply the first ink receiving layer in Example 20. Ink jet recording material was prepared.
  • Example 28 was carried out under the same conditions as Example 20 except that the ink receiving layer coating liquid 14 was used instead of using the ink receiving layer coating liquid 13 to apply the second ink receiving layer in Example 20. Ink jet recording material was prepared.
  • Example 29 An ink jet recording material of Example 29 was produced in the same manner as in Example 20, except that the second ink receiving layer was applied and dried, and then subjected to a soft calender treatment.
  • the ink receiving layer coating liquid 8 was applied as a first ink receiving layer on the support 1 with an air knife coater so that the dry coating amount was 11 g / m 2 , and dried. Then on top of the ink receiving layer, as the second ink-receiving layer, the ink-receiving layer coating solution 13 dry coating weight of the coating with an air knife coater so that the l lg / m 2, and dried, compared The ink jet recording material of Example 10 was produced.
  • An ink jet recording material of Comparative Example 11 was produced under the same conditions as in Example 20, except that the pigment layer coating liquid 17 was used instead of the pigment layer coating liquid 13.
  • the air permeability defined by JIS P8117 of the sheet after coating with the pigment layer was 180 seconds.
  • An ink jet recording material of Comparative Example 12 was produced under the same conditions as in Example 20, except that the pigment layer coating liquid 18 was used instead of the pigment layer coating liquid 13.
  • the air permeability defined by JIS P8117 of the sheet after coating with the pigment layer was 60 seconds.
  • Example 20 Same as Example 20 except that Support 2 was used instead of Support 1 in Example 20 In this way, an inkjet recording material of Comparative Example 13 was produced.
  • the pigment layer coating liquid 13 was coated on the support 1 with an air knife coater and dried so that the dry coating amount was 7 g / m 2 .
  • an ink receiving layer coating liquid 13 was applied using an air knife coater to a dry coating amount of 15 g / m 2 , and dried to obtain an ink jet recording material of Comparative Example 14.
  • the ink jet recording material prepared as described above was coated with black, cyan, magenta, and yellow using MC-10000 manufactured by Seiko Epson Corporation (using a pigment ink, printer setting: MC glossy paper, clear). Solid printing of each color was performed, and image density and ink absorbency were evaluated. The density of the black solid print portion was measured using a densitometer (Macbeth RD918). The higher the value, the better the color development of the ink. The results are shown in Table 2 “ink color development”. Further, the ink absorbency of the printed portion was visually evaluated. Ink absorbency is based on the following criteria Evaluation was made with a numerical value of 1 to 5. If it is 3 or more, there is no practical problem. The results are shown ink Absorption”.
  • Example 20 29 the paper support and the pigment contained therein had an average secondary particle diameter of 1/1 to 5 111 or less, and the secondary particle diameter was 50% by volume or more of the total volume of the pigment.
  • the first ink receiving layer whose amount is 20% by mass or more and 120% by mass or less of the dry coating amount of the pigment layer, and the second ink receiving layer containing alumina hydrate are sequentially laminated to obtain ink.
  • Pigment ink with high glossiness on the surface without causing cracks on the layer surface It becomes possible to obtain an ink jet recording material having both absorptivity and color development.
  • the inorganic ultrafine particles used in the first ink receiving layer are fumed silica
  • the glossiness of the surface without cracks on the surface of the ink receiving layer, the absorption of pigment ink and the color development It is preferred in that respect.
  • the specific surface area of the fumed silica used for the first ink receiving layer by the BET method was lower than that of the anoremina hydrate used for the second ink receiving layer by the BET method.
  • the glossiness of the surface without cracks on the surface of the ink receiving layer and the high absorption and coloring of the pigment ink are high.
  • it is preferable that at least one ink receiving layer other than the first ink receiving layer contains boric acid or borate, since cracks in the coating layer and color development of the image are good.
  • Comparative Example 13 using a support having no air permeability and no ink solvent absorption when the second ink receiving layer was provided, the air in the first ink receiving layer did not escape through the support and the second ink receiving layer did not pass through. Since the ink was removed through the coating surface of the ink receiving layer, a bubble bleeding defect occurred on the surface of the ink receiving layer, and the coating layer was cracked by the influence. In addition, the ink absorbency is insufficient.
  • Comparative Example 14 in which the coating amount ratio of the pigment layer and the ink receiving layer according to the present invention is out of the range the coating layer cracks and the color development of the image is reduced.
  • an ink jet recording material having excellent surface gloss, no cracks on the surface of the ink receiving layer, and having both the coloring property and the absorbing property of the pigment ink. It is clear that can be done.

Landscapes

  • Ink Jet Recording Methods And Recording Media Thereof (AREA)
  • Ink Jet (AREA)

Abstract

L'invention concerne une matière d'impression par jet d'encre empêchant la craquelure superficielle de la couche réceptrice d'encre et présentant concomitamment une absorptivité et une colorabilité d'encre pigmentée satisfaisantes. L'invention se rapporte à une matière d'impression par jet d'encre dont le procédé de production consiste à revêtir successivement au moins une surface principale d'un support papier avec des liquides de revêtement pour une couche pigmentée et au moins une couche réceptrice d'encre, puis à les sécher. Le pigment contenu dans la couche pigmentée présente un diamètre de particule secondaire moyen compris entre 1 et 5 νm et au moins 50 % en volume du pigment, sur la base du volume total, présente un diamètre de particule secondaire compris entre 1,2 et 1,5 νm. La première couche réceptrice d'encre obtenue par revêtement direct de la couche pigmentée comprend au moins des particules ultrafines inorganiques, un liant hydrophile et de l'acide borique ou un sel de borate. La quantité de revêtement sec de la première couche réceptrice d'encre est comprise entre 20 et 120 % en masse sur la base de la quantité de revêtement sec de la couche pigmentée.
PCT/JP2004/012112 2003-11-25 2004-08-24 Matiere d'impression par jet d'encre WO2005051670A1 (fr)

Priority Applications (3)

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CN2004800212207A CN1826232B (zh) 2003-11-25 2004-08-24 喷墨记录材料
DE112004001339T DE112004001339B4 (de) 2003-11-25 2004-08-24 Tintenstrahl-Aufzeichnungsmaterial
US10/564,633 US7713599B2 (en) 2003-11-25 2004-08-24 Inkjet recording material

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2003394439A JP4559062B2 (ja) 2003-11-25 2003-11-25 インクジェット記録材料
JP2003-394439 2003-11-25
JP2004046107A JP2005001373A (ja) 2003-02-26 2004-02-23 インクジェット記録材料
JP2004-046107 2004-02-23

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CN103897517A (zh) * 2012-12-27 2014-07-02 青岛佳艺影像新材料技术有限公司 正喷灯箱胶片涂布液的制取方法

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US8409709B2 (en) * 2010-05-01 2013-04-02 Chu-Yuan Liao Composition of hydrophobic granular play material and its method of manufacture
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US8900677B2 (en) 2011-07-21 2014-12-02 Hewlett-Packard Development Company, L.P. Print medium
JP6188443B2 (ja) * 2013-06-24 2017-08-30 キヤノン株式会社 記録媒体及びその製造方法
JP7219943B2 (ja) * 2018-03-13 2023-02-09 株式会社トンボ鉛筆 感圧転写修正テープ

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